Production of 2-(o-alkylthiophenyl)-1,3-diazocycloalkene hydrohalides

ABSTRACT

Production of new 2-(o-alkylthiophenyl)-1,3-diazacycloalkene hydrohalides by reaction of a benzo-thietane-2-spiro-2&#39;-(1&#39;,3&#39;-diazacycloalkane) with an alkyl halide, and the new 2-(o-alkylthiophenyl)-1,3-diazacycloalkene hydrohalides which are pharmaceuticals, auxiliaries for the textile and rubber industries, plant protection agents and starting materials for the production of pharmaceuticals, plant protection agents and dyes.

This application is a continuation-in-part application of Ser. No.349,915, filed Apr. 11, 1973, now abandoned.

The invention relates to a process for the production of new2-(o-alkylthiophenyl)-1,3-diazacycloalkene hydrohalides by reaction of abenzothietane-2-spiro-2'-(1',3'-diazacycloalkane) with an alkyl halide.

It is an object of this invention to provide a new process for preparingnew 2-(o-alkylthiophenyl)-1,3-diazacycloalkene hydrohalides in goodyields and purity.

Another object of this invention is the new2-(o-alkylthiophenyl)-1,3-diazacycloalkene hydrohalides themselves.

We have found that a 2-(o-alkylthiophenyl)-1,3-diazacycloalkenehydrohalides of the general formula (I): ##STR1## in which R¹ ishydrogen, halogen or an aliphatic radical;

Y is the radical ##STR2## in which the individual radicals R² may beidentical or different and each is hydrogen or an aliphatic radical,

R³ is hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic,or heterocyclic radical, and

X is halogen is obtained advantageously by reacting abenzothietane-2-spiro-2'-(1',3'-diazacycloalkane) of the general formula(II): ##STR3## in which R¹ and Y have the meanings given above with analkyl halide of the general formula (III):

    X--CH--R.sup.3 TM (III)

in which R³ and X have the meanings given above.

When benzothietane-2-spiro-2'-imidazolidine and benzyl chloride are usedthe reaction of the invention may be represented by the followingequation: ##STR4##

The process of the invention gives the new2-(o-alkylthiophenyl)-1,3-diazacycloalkene halides in a good yield andhigh purity.

The starting material (II) is conveniently reacted with the startingmaterial (III) in stoichiometric proportions. Starting material (III)may however be used in excess, for example an excess of up to 1.2 timesthe stoichiometric amount based on starting material (II). The startingmaterial (II) may be prepared for example by the method described inGerman published Application No. 2,034,987 laid open Jan. 20, 1972 (seealso U.S. Pat. No. 3,776,870) by reaction of a halobenzaldehyde compoundwith a diaminoalkane and sulfur.

Preferred starting materials (II) and (III) and consequently preferredend products (I) are those in whose formulae R¹ is hydrogen, bromo,iodo, chloro or alkyl of one to seven carbon atoms, Y is the radical##STR5## the individual radicals R² may be identical or different andeach is hydrogen or alkyl of one to four carbon atoms, R³ is hydrogen,alkyl of one to seven carbon atoms, alkenyl or alkynyl of two to sevencarbon atoms, cyclohexyl, aralkyl of seven to twelve carbon atoms,phenyl or a heterocyclic five-membered or six-membered ring containingone or two nitrogen atoms and/or an oxygen atom and bearing as asubstituent alkyl of one to four carbon atoms, aralkyl of seven to 12carbon atoms or phenyl and X is bromo, iodo or chloro. The heterocyclicring may bear, as a substituent, another five-membered or six-memberedheterocyclic ring containing one or two nitrogen atoms and/or an oxygenatom. They are preferably 1,2,3-oxadiazoles, 1,2,5-oxadiazoles,1,2,4-oxadiazoles and 1,3,4-oxadiazoles. The said radicals and rings mayalso bear groups which are inert under the reaction conditions, forexample alkyl groups, alkoxy groups in each case of one to four carbonatoms, chloro or bromo as substituents on the phenyl radical.

Examples of starting materials (II) are:

benzothietane-2-spiro-2'-imidazolidine,

benzothietane-2-spiro-(4'-ethylimidazolidine),

benzothietane-2-spiro-(4'-isobutylimidazolidine),

benzothietane-2-spiro-(4',5'-dimethylimidazolidine),

benzothietane-2-spiro-(1',3'-diazacyclohexane),

benzothientane-2-spiro(1',3'-diaza-4',6'-diethylcyclohexane) andcorresponding 3-chlorobenzo-(1,2)-thietane, 5-chloro-(1,2-)-thietane,3bromobenzo-(1,2)-thietane, 4-chlorobenzo-(1,2)-thietane,3-methylbenzo-(1,2)-thietane and 4-isobutylbenzo-(1,2)-thietanecompounds.

Examples of alkyl halides suitable as starting materials (III) are asfollows: ethyl chloride, propyl chloride, hexyl chloride, benzylchloride, o-chlorobenzyl chloride, m-chlorobenzyl chloride,p-chlorobenzyl chloride, isopropenyl chloride, methyl chloride,allylchloride, propargyl chloride, methallyl chloride, phenylethylchloride, o,p-dichlorobenzyl chloride, o,o'-dichlorobenzyl chloride,o,m-dichlorobenzyl chloride, p-methoxybenzyl chloride, m-butoxybenzylchloride, cyclohexyl chloride, pyrryl-(2)-methyl chloride,imidazolyl-(2) methyl chloride, pyridinyl-(2) methyl chloride,morpholinyl-(2)-methyl chloride, oxazolyl-(5)-methyl chloride,furfuryl-(2)-methyl chloride, piperazinyl-(2)-methyl chloride,pyrimidinyl-(b 6)-methyl chloride; 5-chloromethyl-1,2,4-oxadiazole,5-chloromethyl-3-m-tolyl-1,2,4-oxadiazole,5-chloromethyl-3-ethyl-1,2,4-oxadiazole,5-chloromethyl-3-methyl-1,2,4-oxadiazole,5-chloromethyl-3-p-toluyl-1,2,4-oxadiazole,5-chloromethyl-3-pyridyl-1,2,4-oxiadiazole,5-chloromethyl-3-m-chloro-p-toluyl-1,2,4-oxidiazole,3-o-chlorophenyl-5-chloromethyl-1,2,4-oxadiazole,3-m-chloromethyl-5-chloromethyl-1,2,4-oxiadiazole,3-p-chloromethyl-5-chloromethyl-1,2,4-oxadiazole and analogous5-chloromethyl-1,2,3-oxadiazoles, 4-chloromethyl-1,2,5-oxadiazoles,3-chloromethyl-1,2,4-oxadiazoles and 5-chloromethyl-1,3,4-oxadiazoles;and corresponding iodides, bromides, bromine compounds and iodinecompounds.

The reaction is carried out as a rule at a temperature of from 10° to150° C., preferably from 50° C. to 100° C., at atmospheric orsuperatmospheric pressure, continuously or batchwise. It is convenientto use an organic solvent which is inert under the reaction conditions,for example an aromatic hydrocarbon such as benzene or toluene; analkanol such as methanol, ethanol, propanol or a butanol; a glycol ethersuch as glycol monomethyl ether or glycol monoethyl ether; orappropriate mixtures. A ratio of from 5 to 20 moles of solvent per moleof starting material (II) is preferred.

The reaction may be carried out as follows: the starting materials (II)and (III), with or without a solvent, are heated to the reactiontemperature. The mixture is then allowed to react at the reactiontemperature for fron one to five hours. The end product is thenseparated by a conventional method, for example by crystallization orfiltration of the mixture. If necessary the end product may be purifiedby recrystallization.

The new compounds which can be prepared by the process of the inventionare pharmaceuticals, auxiliaries for the textile and rubber industries,plant protection agents and also valuable starting materials for theproductions of pharmaceuticals, plant protection agents and dyes. Inparticular when they are administed perorally or intravenously theycause prolonged increase in blood pressure and affect the centralnervous system. They are capable of neutralizing eyelid paralysis inmice caused by reserpin and they increase excretion of urine in rats.

Examples of pharmaceutical properties are given in the following Table.The blood pressure-raising action is detected in the conventional manneron rats narcotized with urethane. Blood pressure is measured from thecarotid artery by means of Statham elements. Intravenous injection ofthe end product (I) is effected through a cannula inserted into thejugular vein. The increase in blood pressure after administration of thetest substances is measured in mm of Hg and the duration of action inminutes. The tests are discontinued thirty minutes after administrationof the test substance.

The columns in the following Table are as follows:

I=Z

II=R³

III=approximate toxicity in mg/kg administered orally

IV=approximate toxicity in mg/kg administered intravenously

V=maximum increase in blood pressure in mm of Hg after intravenousinjection of 1 mg/kg

VI=duration of action in minutes

VII=remarks.

                                      TABLE                                       __________________________________________________________________________     ##STR6##                                                                     I            II            III                                                                              IV V VI VII                                     __________________________________________________________________________     ##STR7##    C.sub.6 H.sub.5                                                                             200                                                                              30 35                                                                              >30                                         ##STR8##                                                                                   ##STR9##     200                                                                              30 47                                                                              >30                                         ##STR10##                                                                                  ##STR11##    100                                                                              50 28                                                                              >30                                         ##STR12##                                                                                  ##STR13##    100                                                                              30 41                                                                                8                                         ##STR14##                                                                                  ##STR15##    200                                                                              30 23                                                                              >30                                         ##STR16##                                                                                  ##STR17##    200                                                                              200                                                                              --                                                                              -- marked dilation of coronary                                                   vessels                                  ##STR18##                                                                                  ##STR19##    100                                                                              50 15                                                                               26                                         ##STR20##                                                                                  ##STR21##    200                                                                              100                                                                              --                                                                              -- marked dilation of coronary             __________________________________________________________________________                                          vessels                             

The following Examples illustrate the invention. The parts given in thefollowing Examples are by weight.

EXAMPLE 1 2-(2'-methylthiophenyl)-Δ2-imidazoline hydroiodide ##STR22##

44.5 Parts of benzothietane-2-spiro-2'-imidazolidine is reacted with35.5 parts of methyl iodide in 400 parts of methanol. The reactionmixture is stirred for three hours at 60° C. and then concentrated tohalf its volume, cooled and suction filtered. The yield is 68 parts (85%theory) and the melting point is 212° C.

EXAMPLE 2 2-(2'-allylthiophenyl)-Δ2-imidazoline hydrobromide ##STR23##

44.5 Parts of benzothietane-2-spiro-2'-imidazolidine is reacted with 30parts of allyl bromide in 400 parts of methanol. The reaction mixture isstirred for 3 hours at 60° C., then concentrated to half its volume,cooled and suction filtered. The yield is 62 parts (83% of theory) andthe melting point is 132° C.

EXAMPLE 3 2-(2'-propargylthiophenyl)-Δ2-imidazoline hydrobromide##STR24##

44.5 Parts of benzothietane-2-spiro-2'-imidazolidine is reacted with 30parts of propargyl bromide in 400 parts of methanol. The reactionmixture is stirred for three hours at 60° C., concentrated, cooled andsuction filtered. The yield is 69 parts (93% of theory) and the meltingpoint is 185° C.

EXAMPLE 4 2-(2'-benzylthiophenyl)-Δ2-imidazoline hydrochloride ##STR25##

44.5 Parts of benzothientane-2-spiro-2'-imidazolidine is reacted with31.6 parts of benzyl chloride in 400 parts of methanol. The reactionmixture is stirred for three hours at 60° C., concentrated, cooled andsuction filtered. The yield is 64 parts (81% of theory) and the meltingpoint is 217° C.

EXAMPLE 5 2-[2'-(4"-chlorobenzylthio)-phenyl]-Δ2-imidazolinehydrochloride ##STR26##

44.5 Parts of benzothientane-2-spiro-2'-imidazolidine is reacted with40.3 parts of 4-chlorobenzyl chloride in 400 parts of methanol. Thereaction mixture is stirred for 3 hours at 60° C., concentrated, cooledaud suction filtered. The yield is 80 parts (94% of theory) and themelting point is 177° C.

EXAMPLE 6 2-[2'-(2"-chlorobenzylthio)-phenyl]-Δ2-imidazolinehydrochloride ##STR27##

44.5 Parts of benzothientane-2-spiro-2'-imidazolidine is reacted with40.3 parts of 2-chlorobenzyl chloride in 400 parts of methanol. Thereaction mixture is stirred for 3 hours at 60° C., concentrated, cooledand suction filtered. The yield is 67 parts (80% of theory) and themelting point is 202° C.

EXAMPLE 7 2-[2'-(2"-dichlorobenzylthio)-phenyl]-Δ2-imidazolinehydrochloride ##STR28##

44.5 Parts of benzothientane-2-spiro-2'-imidazolidine is reacted with 49parts of 2,5-dichlorobenzyl chloride in 400 parts of methanol. Thereaction mixture is stirred for three hours at 60° C., concentrated,cooled and suction filtered. The yield is 76 parts (81% of theory) andthe melting point is 236° C. (with decomposition).

EXAMPLE 8 2-[2'-(2",6"-dichlorobenzylthio)-phenyl]-Δ2-imidazolinehydrochloride ##STR29##

44.5 Parts of benzothietane-2-spiro-2'-imidazolidine is reacted with 49parts of 2,6-dichlorobenzyl chloride in 400 parts of methanol. Thereaction mixture is stirred for 3 hours at 60° C., concentrated, cooledand suction filtered. The yield is 80 parts (86% of theory) and themelting point is 214° C.

EXAMPLE 9 2-[2'-(3"-methyl-1",2",4"-oxadizolyl-5"-methylthio)-phenyl]-Δ2-imidazoline hydrochloride##STR30##

44.5 Parts of benzothietane-2-spiro-2'-imidazolidine is reacted with 33parts of 3-methyl-5-chloromethyl-1,2,4-oxadiazole in 400 parts ofmethanol. The reaction mixture is stirred for 3 hours at 60° C.,concentrated, cooled and suction filtered. The yield is 58 parts (75% oftheory) and the melting point is 225° to 230° C.

EXAMPLE 10 2-(2'-methylthiophenyl)-tetrahydropyrimidine hydroiodide##STR31##

48 Parts of benzothietane-2-spiro-2',1', 3'-diazacyclohexane is reactedwith 35.5 parts of methyl iodide in 400 parts of methanol. The reactionmixture is stirred for three hours at 60° C., concentrated, cooled andsuction filtered. The yield is 71 parts (85% of theory) and the meltingpoint is 257° C.

EXAMPLE 11 2-(2'-methallylthiophenyl)-tetrahydropyrimidine hydrochloride##STR32##

48 Parts of benzothietane-2-spiro-2',1',3'-diazacyclohexane is reactedwith 22.6 parts of methallyl chloride in 400 parts of methanol. Thereaction mixture is stirred for three hours at 60° C., concentrated,cooled and suction filtered. The yield is 58 parts (82% of theory) andthe melting point is 194° C.

EXAMPLE 12 2-(2'-benzylthiophenyl)-tetrahydropyrimidine hydrochloride##STR33##

48 Parts of benzothietane-2-spiro-2',1',3'-diazacyclohexane is reactedwith 31.6 parts of benzyl chloride in 400 parts of methanol as describedin Example 11. The yield is 70 parts (88% of theory) and the meltingpoint is 240° C. with decomposition.

EXAMPLE 13 2-[2'-(2"-chlorobenzylthio)-phenyl]-tetrahydropyrimidinehydrochloride ##STR34## 48 Parts of benzothietane-2-spiro-2',1',3'-diazacyclohexane is reacted with 40 parts of 2-chlorobenzyl chloridein 400 parts of methanol as described in Example 11. The yield is 74parts (84% of theory) and the melting point is 215° C. EXAMPLE 142-[2'-(3"-chlorobenzylthio)-phenyl]-tetrahydropyrimidine hydrochloride##STR35##

48 parts of benzothietane-2-spiro-2',1',3'-diazacyclohexane is reactedwith 40 parts of 3-chlorobenzyl chloride in 400 parts of methanol asdescribed in Example 11. The yield is 76 parts (87% of theory) and themelting point is 224° C.

EXAMPLE 15 2-[2'-(4"-chlorobenzylthio)-phenyl]-tetrahydropyrimidinehydrochloride ##STR36##

48 Parts of benzothietane-2-spiro-2',1',3'-diazacyclohexane is reactedwith 40 parts of 4-chlorobenzyl chloride in 400 parts of methanol asdescribed in Example 11. The yield is 68 parts (77% of theory) and themelting point is 252° C.

EXAMPLE 16 2-[2'-(2",4"-dichlorobenzylthio)-phenyl]-tetrahydropyrimidinehydrochloride ##STR37##

48 Parts of benzothietane-2-spiro-2',1', 3'-diazacyclohexane is reactedwith 40 parts of 2,4-dichlorobenzyl chloride in 400 parts of methanol asdescribed in Example 11. The yield is 78 parts (80% of theory) and themelting point is 238° C.

EXAMPLE 17 2-[2'-(2",5"-dichlorobenzylthio)-phenyl]-tetrahydropyrimidinehydrochloride ##STR38## 48 Parts ofbenzothietane-2-spiro-2',1',3'-diazacyclohexane is reacted with 49 partsof 2,5-dichlorobenzyl chloride in 400 parts of methanol as described inExample 11. The yield is 82 parts (85% of theory) and the melting pointis 242° C. EXAMPLE 182-[2'-(2",6"-dichlorobenzylthio)-phenyl]-tetrahydropyrimidinehydrochloride ##STR39##

48 Parts of benzothietane-2-spiro-2',1',3'-diazacyclohexane is reactedwith 49 parts of 2,6-dichlorobenzyl chloride in 400 parts of methanol asin Example 11. The yield is 74 parts (76% of theory) and the meltingpoint is 250° C.

EXAMPLE 192-[2'-(3"-p-methylphenyl-1",2",4"-oxadiazolyl-5"-methylthio)-phenyl]-tetrahydropyrimidinehydrochloride ##STR40##

48 Parts of benzothientane-2-spiro-2',1',3'-diazacyclohexane is reactedwith 52 prts of 3-p-methylphenyl-5-chloromethyl-1,2,4-oxadiazole in 400parts of methanol as in Example 11. The yield is 73 parts (73% oftheory) and the melting point is 227° to 228° C.

EXAMPLE 202-[2'-3"-(3"'-chloro-4"'-methylphenyl)-1",2",4"-oxadiazolyl-5"-methylthio-phenyl]-tetrahydropyrimidinehydrochloride ##STR41##

48 Parts of benzothietane-2-spiro-2',1',3'-diazacyclohexane is reactedwith 58.6 parts of3-(3'-chloro-4'-methylphenyl)-5-chloromethyl-1,2,4-oxadiazole in 400parts of methanol in the manner described in Example 11. The yield is 79parts (74% of theory) and the melting point is 260° C. withdecomposition.

EXAMPLE 212-[2'-(3"-m-tolyl-1",2",4"oxadiazolyl-5"-methylthio)-phenyl]-tetrahydropyrimidinehydrochloride ##STR42##

48 Parts of benzothietane-2-spiro-2',1', 3'-diazacyclohexane is reactedwith 52 parts of 3-(m-tolyl)-5-chloromethyl-1,2,4-oxadiazole in 400parts of methanol as described in Example 11. The yield is 61 parts (61%of theory) and the melting point is 232° to 235° C.

EXAMPLE 22 2-[2'-(4"-chlorobenzylthio)-5'-chlorophenyl]-imidazolinehydrochloride ##STR43##

53 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazolidine is reactedwith 40 parts of p-chlorobenzyl chloride in 500 parts of methanol asdescribed in Example 11. The yield is 84 parts (91% of theory) and themelting point is 248° to 250° C.).

EXAMPLE 23 2-(2'-methallylthio-5'-chlorophenyl)-imidazolinehydrochloride ##STR44##

32 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazolidine is reacted in400 parts of methanol with 13.6 parts of methallyl chloride as describedin Example 11. The yield is 42 parts (92% of theory) and the meltingpoint is 228° C.

EXAMPLE 24 2-(2'-benzylthio-5'-chlorophenyl)-imidazolidine hydrochloride##STR45##

32 parts of 4-chlorobenzothietane-2spiro-2'-imidazolidine is reactedwith 19 parts of benzyl chloride in 300 parts of methanol as describedin Example 11. The yield is 43 parts (84% of theory) and the meltingpoint is 260° C. with decomposition.

EXAMPLE 25 2-[4'-(2"-chlorobenzylthio)-5'-chlorophenyl]-imidazolinehydrochloride ##STR46##

32 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazoline is reacted with26 parts of 2-chlorobenzyl chloride in 300 parts of methanol. The yieldis 52 parts (90% of theory) and the melting point is 260° . withdecomposition.

EXAMPLE 26 2-[2'-(3"-chlorobenzylthio)-5'-chlorophenyl]-imidazolinehydrochloride ##STR47##

32 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazolidine is reactedwith 26 parts of 3-chlorobenzyl chloride in 300 parts of methanol, asdescribed in Example 11. The yield is 49 parts (85% of theory ) and themelting point is 255° C.

EXAMPLE 27 2-[2'-(2",4"-dichlorobenzylthio)-5'-chlorophenyl]-imidazolinehydrochloride ##STR48##

32 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazolidine is reacted in300 parts of methanol with 29.5 parts of 2,4-dichlorobenzyl chloride inthe manner described in Example 11. The yield is 56 parts (90% oftheory) and the melting point is 236° C.

EXAMPLE 28 2-[2'-(2",5"-dichlorobenzylthio)-5'-chlorophenyl]-imidazolinehydrochloride ##STR49##

32 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazolidine is reacted asdescribed in Example 11 with 29.5 parts of 2,5-dichlorobenzyl chloridein 300 parts of methanol. The yield is 53 parts (86% of theory) and themelting point is 260° C. with decomposition.

EXAMPLE 292-[2'-(3'-methyl-1",2",4"-oxadiazolyl-5"-methylthio)-5'-chlorophenyl]-imidazolinehydrochloride ##STR50##

In the manner described in Example 11 53 parts of4-chlorobenzothietane-2-spiro-2'-imidazolidine is reacted with 33 partsof 3-methyl-5-chloromethyl-1,2,4-oxadiazole in 400 parts of methanol.The yield is 70 parts (81% of theory) and the melting point is 250° to255° C. with decomposition.

EXAMPLE 302-[2'-(3"-p-tolyl-1",2",4"-oxadiazolyl-5"-methylthio)-5'-chlorophenyl]imidazolinehydrochloride ##STR51##

53 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazolidine is reactedwith 52 parts of 2-(4'-methylphenyl)-5-chloromethyl-1,2,4-oxidiazole asdescribed in Example 11. The yield is 82 parts (78% of theory) and themelting point is 270° C. with decomposition.

EXAMPLE 312-[2'-(3'-(o-chlorophenyl)-1,",2",4"-oxadiazolyl-5"-methylthio)-5'chlorophenyl]-imidazoline hydrochloride ##STR52##

53 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazolidine is reactedwith 56 parts of 3-(o-chlorophenyl)-5-chloromethyl-1,2,4-oxadiazole in400 parts of methanol as described in Example 11. The yield is 96 parts(88% of theory) and the melting point is 265° to 270° C.

EXAMPLE 322-[2'-(3"'-chloro-4"'-methylphenyl)-1",2",4"-oxadiazolyl-5"-methylthio)-5'-chlorophenyl]-imidazolinehydrochloride: ##STR53##

53 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazolidine is reactedwith 58.6 parts of3-(3'-chloro-4'-methylphenyl)-5-chloromethyl-1,2,4-oxadiazole in 400parts of methanol as described in Example 11. The yield is 89 parts (80%of theory) and the melting point is 260° C. with decomposition.

EXAMPLE 332-[2'-(5"-methyl-1",2",4"-oxadiazolyl-3"-methylthio)-5'-chlorophenyl]-imidazolinehydrochloride ##STR54##

24 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazolidine is reacted in200 parts of methanol with 15 parts of3-chloromethyl-5-methyl-1,2,4-oxadiazole as described in Example 11. Theyield is 32 parts (82% of theory) and the melting point is 213° to 215°C.

EXAMPLE 342-[2'-(2"-p-methoxyphenyl-1",3",4"-oxadiazolyl-5"-methylthio)-5'-chlorophenyl]-imidazolinehydrochloride ##STR55##

10.6 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazolidine is reactedin 200 parts of methanol with 11.2 parts of2-p-methoxyphenyl-5-chloromethyl-1,3,4-oxadiazole as described inExample 11. The yield is 18 parts (83% of theory) and the melting pointis 272° C.

EXAMPLE 352-[2'-(2"-(2"',5"'-dichlorophenyl)-1",3",4"-oxadiazolyl-5"-methylthio)-5'-chlorophenyl]-imidazolinehydrochloride ##STR56##

21.2 parts of 4- chlorobenzothietane-2-spiro-2'-imidazolidine is reactedin 500 parts of methanol with 26.3 parts of 2-(2', 5'-dichlorophenyl)-5-chloromethyl-1,3,4-oxadiazole as described in Example 11. The yield is41 parts (86% of theory) and the melting point is 328° to 330° C.

EXAMPLE 362-[2'-(3"-ethyl-1",2",4"-oxadiazolyl-5"-methylthio)-5'-chlorophenyl]-imidazolinehydrochloride ##STR57##

10.6 Parts of 4-chlorobenzothietane-2-spiro-2'-imidazolidine is reactedin 200 parts of methanol with 7.3 parts of3-ethyl-5-chloromethyl-1,2,4-oxadiazole as described in Example 11. Theyield is 15 parts (84% of theory) and the melting point is 120° to 122°C.

EXAMPLE 372-[2'-(3"-pyridyl-1",2",4"-oxadiazolyl-5"-methylthio)-phenyl]-imidazolinehydrochloride ##STR58##

18 Parts of benzothietane-2-spiro-2'-imidazolidine is reacted with 20parts of 3-pyridyl-5-chloromethyl-1,2,4-oxadiazole in 400 parts ofmethanol as described in Example 11. The yield is 30 parts (79% oftheory) and the melting point is 268° to 270° C.

EXAMPLE 382-[2'-(1",2",4"-oxadiazolyl-5"-methylthio)-phenyl]-Δ2-imidazolinehydrochloride ##STR59##

44.5 Parts of benzothietane-2spiro-2'-imidazolidine is reacted with 29.6parts of 5-chloromethyl-1,2,4-oxadiazole in 400 parts of methanol. Thereaction mixture is stirred for 3 hours at 60° C., concentrated, cooledand suction filtered. The yield is 61 parts (82% of theory) and themelting point is 238° to 240 ° C.

The invention is hereby claimed as follows:
 1. A process for theproduction of a 2-(o-alkylthiophenyl)-1,3-diazacycloalkene hydrohalideof the formula ##STR60## in which R¹ is hydrogen, bromo, iodo, chloro oralkyl of one to seven carbon atoms, Y is the divalent radical ##STR61##wherein each R² is hydrogen or alkyl of one to four carbon atoms, R³ ishydrogen, alkyl of one to seven carbon atoms, alkenyl or alkynyl of twoto seven carbon atoms each, cyclohexyl, aralkyl of seven to twelvecarbon atoms, phenyl or a heterocyclic member selected from the groupconsisting of pyrryl-(2); imidazolyl-(2); pyridinyl-(2);morpholinyl-(2); oxazolyl-(5); furfuryl-(2); piperazinyl-(2);pyrimidinyl-(6); 1,2,3-oxadiazolyl-(4) or -(5), 1,2,4-oxadiazolyl-(3) or-(5), or 1,2,5-oxadiazolyl-(3) or -(4), and the same oxadiazolyl ringssubstituted once by methyl, ethyl, phenyl or pyridyl; with the provisothat phenyl may further bear an inert substituent selected from thegroup consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4carbon atoms, chloro or bromo, and X is bromo, iodo or chloro, whichcomprises: reacting a benzothietane-2-spiro-2'-(1',3'-diazacycloalkane)of the formula ##STR62## in which R¹ and Y have the meanings givenabove, with an alkyl halide of the formula:

    X--CH.sub.2 --R.sup.3                                      (III)

in which R³ and X have the meanings given above, at a temperature offrom 10° to 150° C.
 2. A process as claimed in claim 1 wherein thereaction is carried out in the presence of an inert organic solvent. 3.A process as claimed in claim 2 wherein said inert organic solvent isselected from the group consisting of aromatic hydrocarbons, alkanols,glycol ethers or mixtures thereof.
 4. A process as claimed in claim 3wherein said solvent is benzene or toluene.
 5. A process as claimed inclaim 3 wherein said solvent is methanol, ethanol, propanol or butanol.6. A process as claimed in claim 3 wherein said solvent is glycolmonomethyl ether or glycol monoethyl ether.
 7. A process as claimed inclaim 3 wherein said solvent is methanol.